JP2001181340A - Chlorinated vinyl chloride resin, its production method, and its molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chlorinated vinyl chloride resin excellent in heat stability and gelling properties, its production method, and its molded article. SOLUTION: This chlorinated vinyl chloride resin is produced by chlorinating a vinyl chloride resin of which the peak ratio (chlorine element peak × 2/carbon element peak) in the 1S bond energy value (eV) of carbon atom and chlorine atom is higher than 0.6 in the particle surface analysis by electron-spectroscopic chemical analysis(ESCA). The chlorinated vinyl chloride resin is characterized in that the chlorine content is 60-72 wt.%; that the porosity measured by the mercury forcing-in method under a pressure of 196 MPa is 30-40 vol.%; and that the volume of micropores with 0.001-0.1 μm-size accounts for 2-15 vol.% of the volume of total micropores in the micropore volume distribution measured by the mercury forcing-in method under a pressure of 0-196 MPa.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chlorinated vinyl chloride resin, a method for producing the same, and a molded product thereof.

[0002]

2. Description of the Related Art Conventionally, vinyl chloride resins (hereinafter referred to as P
VC) is used in many fields as a material having excellent mechanical strength, weather resistance and chemical resistance. However, since the heat resistance is poor, a chlorinated vinyl chloride resin (hereinafter referred to as C) in which the heat resistance is improved by chlorinating PVC.
PVC) has been developed. Since PVC has a low heat distortion temperature and the maximum usable temperature is around 60 to 70 ° C, it cannot be used for hot water, whereas CPVC has a heat deformation temperature 20 to 40 ° C higher than PVC, It can be used for hot water, and is suitably used for heat-resistant pipes, heat-resistant joints, heat-resistant valves, heat-resistant plates, and the like.

However, since CPVC has a high heat deformation temperature, a high temperature and a shearing force are required for gelling at the time of moldability, and it tends to be decomposed and colored during molding. Therefore, CPVC has a narrow forming width,
In many cases, the product is produced in an insufficient gelation state, and it cannot be said that the performance of the material can be sufficiently exhibited. Therefore, it is desired to improve the thermal stability at the time of molding the CPVC and to improve the molding processability.

[0004] In order to solve such a problem, there has been proposed a method for producing a CPVC having good thermal stability. For example, Japanese Patent Publication No. 45-30833 discloses that chlorine having an oxygen concentration of 0.05 to 0.35% by volume is supplied at a specific flow rate and chlorinated at a temperature of 55 to 80 ° C. It is stated that good CPVC can be obtained. However, due to the high oxygen concentration and the reaction at a low temperature, the thermal stability is not particularly excellent, and it cannot withstand long-term extrusion and injection molding.

For example, Japanese Patent Application Laid-Open No. 9-328518 discloses a method of chlorinating under ultraviolet irradiation using chlorine having an oxygen concentration of 200 ppm or less. However, due to the low-temperature reaction caused by UV irradiation,
A CPVC resin having remarkably excellent thermal stability has not been obtained. Further, in Japanese Patent Application Laid-Open No. 6-32822,
Supplying chlorine containing 100 ppm of oxygen to 110-1
A method for chlorination at a temperature of 35 ° C. has been proposed. According to this method, CPVC having excellent thermal stability can be obtained due to chlorination at a high temperature by thermal chlorination, and the chlorination reaction proceeds smoothly. However, due to the effect of thermal energy due to the high-temperature reaction, the voids inside the particles are reduced, and it is difficult to develop sufficient gelation during molding. It is necessary to generate heat.

In the case of molded articles such as heat-resistant pipes, heat-resistant joints, heat-resistant valves, heat-resistant plates, etc., high-temperature steam of 100 ° C. or more is generated or heated to 100 ° C. or more due to malfunction of safety devices. When a chemical solution is injected,
There is a need for molded articles such as pipes, joints, and plates having higher heat resistance and chemical resistance than conventional hot water supply pipes, hot water supply pipe joints, and storage tanks.

[0007] Therefore, in order to further improve the heat resistance of the molded article, it has been proposed to mold using a CPVC resin having a higher chlorine content than conventional CPVC.
However, as described above, the heat deformation temperature is high, and high temperature and shearing force are required to gel at the time of moldability, and it is easy to decompose at the time of moldability. In many cases, it could not be said that physical properties such as impact strength were sufficiently exhibited.

[0008] In the CPVC pipe, as the gelation becomes insufficient, the water absorption increases and the long-term creep performance decreases. When the amount of water absorption is large, the diametrical expansion due to the water absorption increases, and expansion and destruction are likely to occur. Further, when the long-term creep performance is reduced, rupture or the like is likely to occur, and it becomes difficult to use the tube as a tube. In the lining pipe,
Cracking of the inner surface or blockage in the pipe due to water absorption expansion occurs. For this reason, a sufficiently gelled tube is required.

Furthermore, CPVC has a disadvantage that the surface (inner surface) of the pipe is inferior in smoothness due to its higher viscosity and longer stress relaxation time than ordinary PVC. If the inner surface of the tube is inferior in smoothness, stagnation tends to occur due to the effects of irregularities, and recent propagation and accumulation of garbage tend to occur.
It is difficult to use in ultrapure water pipes and lining pipes for plants. In general, in order to impart smoothness to a molded product, measures are taken to increase the molding resin temperature and the mold temperature or to increase the residence time in the mold. Means that the resin is easily decomposed due to heat history,
In some cases, there was a problem in long-run performance (continuous manufacturing).

In order to solve such a problem, for example, Japanese Patent Application Laid-Open No. Sho 49-6080 discloses a method using an ionic emulsifier, a water-soluble metal and a water-soluble polymer, Discloses a method of chlorinating a PVC resin composed of an aggregate comprising basic particles. However, in this method, although the gelling performance at the time of molding is improved, the heat resistance and the gelling performance are not yet sufficiently satisfied.

[0011]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide a chlorinated vinyl chloride resin excellent in thermal stability and gelling property, a method for producing the same, and a molded article thereof. I do.

[0012]

The chlorinated vinyl chloride resin according to the first aspect of the present invention (hereinafter referred to as "the present invention 1") is a chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin. The vinyl resin has a peak ratio (chlorine element peak × 2 / carbon element peak) in 1S bond energy value (eV) of carbon atom and chlorine atom in particle surface analysis by electron spectrochemical analysis (ESCA).
The chlorinated vinyl chloride resin has a chlorine content of 60 to 72% by weight, a porosity measured at a pressure of 196 MPa by a mercury intrusion method of 30 to 40% by volume, and a mercury intrusion method. In the pore volume distribution measured at a pressure of 0 to 196 MPa, 0.001 to 0.1 μm
Is 2 to 15% by volume of the total void volume. Hereinafter, the present invention will be described in detail.

The PVC of the present invention refers to a vinyl chloride monomer (hereinafter referred to as VCM) alone, or VCM and VCM.
It is a resin obtained by polymerizing a mixture with another monomer copolymerizable with a known method. Other monomers copolymerizable with the VCM are not particularly limited, and include, for example, alkyl vinyl esters such as vinyl acetate; α-monoolefins such as ethylene and propylene; vinylidene chloride; and styrene. These may be used alone, 2
More than one species may be used in combination.

The above-mentioned PVC is obtained by an electron spectrochemical analysis (ESC).
In the particle surface analysis according to A), the peak ratio (chlorine element peak × 2 / carbon element peak) at a 1S bond energy value (eV) between a carbon atom and a chlorine atom is limited to a value exceeding 0.6, preferably It is more than 0.7. When the peak ratio is 0.6 or less, it is considered that an additive such as a dispersant is adsorbed on the surface of the PVC particles.
A problem arises in the formability of C, and the thermal stability becomes poor. Among the PVCs having a peak ratio of more than 0.6, particles (hereinafter, referred to as skin) having a small skin (hereinafter, referred to as skin) area on the surface of the PVC particles and exposing a fine structure (primary particles) inside the particles. Less PVC). When the energy ratio is the same, it is preferable to use skinless PVC.

The atomic abundance ratio of the chemical structure of PVC is as follows:
Chlorine atom: carbon atom = 1: 2 (when the terminal structure and branching are not considered), and the peak ratio (chlorine element peak × 2 / carbon element peak) in the above 1S binding energy value (eV) is 0 to 1. Becomes If the peak ratio is 0, PV
This means that the surface of the C particles is covered with a substance other than PVC and containing no chlorine. If the peak ratio is 1, the surface of the PVC particles is completely covered with only the PVC component. Means that.

The CPVC of the present invention is defined by a chlorine content, a porosity, and a pore volume of 0.001 to 0.1 μm. That is, the chlorine content of the CPVC is 60 to
It is limited to 72% by weight, preferably 63 to 70% by weight. When the chlorine content is less than 60% by weight, the improvement in heat resistance is insufficient, and when it exceeds 72% by weight, molding processing becomes difficult and gelation becomes insufficient.

The porosity of the above-mentioned CPVC is measured at a pressure of 196 MPa by a mercury intrusion method.
And preferably from 31 to 38% by volume. If the porosity is less than 30% by volume, the gelation at the time of molding becomes slow, which is not preferable for molding. On the other hand, if the porosity exceeds 40% by volume, biting into the screw during molding becomes worse,
Poor gelling properties.

The pore volume of the above-mentioned CPVC of 0.001 to 0.1 μm is set to a value of 0 to 196 MPa by a mercury intrusion method.
In the pore volume distribution measured in the above, 2 to 1 of the total void volume
5% by volume, preferably 3 to 13% of the total void volume
% By volume. Since the pore diameter in the resin particles is a function of the pressure of the mercury injected into the pores of the resin, the pore diameter distribution can be measured by continuously measuring the injection pressure and the mercury weight. become. 0.001-0.1μ
m is less than 2% by volume of the total void volume,
Since the ratio of micropores inside the particles is small, the gelling property during molding is inferior. If it exceeds 15% by volume, the diffusion of chlorine during chlorination is not performed in a well-balanced manner, and the chlorination degree distribution in the particles increases Too poor thermal stability.

According to the second aspect of the invention (hereinafter referred to as the second aspect)
Chlorinated vinyl chloride resin
A chlorinated vinyl chloride resin obtained by
Vinyl resin is measured by electron spectrochemical analysis (ESCA)
In particle surface analysis, 1S bond between carbon atom and chlorine atom
Peak ratio at combined energy value (eV)
Peak x 2 / carbon element peak) exceeds 0.6
The chlorinated vinyl chloride resin has a chlorine content of 6
0-72% by weight, at a pressure of 196MPa by mercury intrusion method
The measured porosity is 30 to 40% by volume, and the BET specific surface
Product is 2-12m ^Two/ G.

The peak ratio in the ESCA analysis of the PVC of the present invention 2 is the same as that of the present invention 1. Further, the chlorine content and the porosity of the CPVC of the second invention are the same as those of the first invention.

The BET specific surface area value of the CPVC of the present invention 2 is limited to ^{2 to} 12 m ² / g, preferably 3 to 1 m ² / g.
0 m @ 2 / g. If the BET specific surface area is less than 2 m ² / g, the ratio of micropores inside the particles is small, so that during the molding process, melting in the particles hardly occurs and the gelling property is poor, and conversely, the BET specific surface area is 12 m ² / g. When it exceeds, frictional heat is generated from the inside rapidly and thermal stability during molding is inferior.

The chlorinated vinyl chloride resin according to the invention of claim 3 (hereinafter referred to as the present invention 3) is a chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin, wherein the vinyl chloride resin is In particle surface analysis by electron spectrochemical analysis (ESCA), 1S of carbon atom and chlorine atom
The peak ratio (chlorine element peak × 2 / carbon element peak) in the binding energy value (eV) exceeds 0.6, and the chlorinated vinyl chloride resin has a chlorine content of 6%.
0 to 72% by weight, a porosity of 30 to 40% by volume measured at a pressure of 196 MPa by a mercury intrusion method, and a pore volume distribution of 0.001 to 0.1 μm in a pore volume distribution measured at a pressure of 0 to 196 MPa by a mercury intrusion method. The void volume is 2 to 15% by volume of the total void volume, and the absorbance (cell length 1 cm, measurement temperature 23 ° C.) of a 1 g / kg tetrahydrofuran solution is 0.8 or less at a wavelength of 235 nm.

The peak ratio in the ESCA analysis of the PVC of the third invention is the same as that of the first invention. Further, the chlorine content, porosity, and 0.001 to 0.
The void volume of 1 μm is the same as that of the first embodiment.

Absorbance of 1 g / kg tetrahydrofuran solution of CPVC of the present invention 3 (cell length 1 cm, measurement temperature 23
C) is limited to 0.8 or less at a wavelength of 235 nm, and is preferably 0.2 or less. In the above-mentioned CPVC, the heterogeneous structure in the molecular chain at the time of the chlorination reaction is quantified based on the value of the absorbance and used as an index of thermal stability. An ultraviolet absorption spectrum was measured, and a heterogeneous structure in CPVC,-
CH = CH-C (= O)-, -CH = CH-CH = CH
-Absorbance at a wavelength of 235 nm with absorption (cell length 1c
m, measurement temperature 23 ° C.). The reason for limiting the absorbance to 0.8 or less is as follows.
That is, since the chlorine atom attached to the carbon next to the double bond is unstable, dehydrochlorination starts from there. That is, as the value of the absorbance is larger, dehydrochlorination is more likely to occur and the thermal stability is lower. Absorbance value of 0.8
When the value exceeds, the influence of the heterogeneous structure in the molecular chain becomes large, and as a result, the thermal stability becomes poor.

Examples of the chlorination method for reducing the absorbance of a 1 g / kg tetrahydrofuran solution to 0.8 or less include a thermal chlorination method and a photo chlorination method, but are not particularly limited. Is preferably used. In order to develop high thermal stability by high-temperature reaction, oxidation (formation of a heterogeneous structure represented by a carbonyl group) during the chlorination reaction is less likely to occur at higher temperatures (the higher the temperature, the more the reaction equilibrium moves in a direction to suppress the formation). Is caused by Specifically, the reaction temperature is 70 to 1
35 ° C is preferable, and 90 to 125 ° C is more preferable. In the case of thermal chlorination, if the reaction temperature is lower than 70 ° C., the reaction rate of chlorination is low. Therefore, in order to advance the reaction, it is necessary to add a large amount of a reaction catalyst represented by peroxide. Also, the thermal stability of the obtained resin may be poor. In the case of photochlorination, when the reaction temperature is lower than 70 ° C., chlorine is easily dissolved in water, and oxygen is easily generated in the reaction tank. As a result, the resulting resin may have poor thermal stability. Conversely, if the reaction temperature exceeds 135 ° C., the resin may be degraded by thermal energy, and the resulting CP
VC may be colored

The chlorinated vinyl chloride resin according to the invention of claim 4 (hereinafter referred to as Invention 4) is a chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin. In particle surface analysis by electron spectrochemical analysis (ESCA), 1S of carbon atom and chlorine atom
The peak ratio (chlorine element peak × 2 / carbon element peak) in the binding energy value (eV) exceeds 0.6, and the chlorinated vinyl chloride resin has a chlorine content of 6%.
0 to 72% by weight, a porosity of 30 to 40% by volume measured at a pressure of 196 MPa by a mercury intrusion method, a BET specific surface area of ² to 12 m ² / g, and an absorbance of a 1 g / kg tetrahydrofuran solution (cell length 1 cm, measurement temperature 23 ° C.) is 0.8 or less at a wavelength of 235 nm.

The peak ratio in the ESCA analysis of the PVC of the present invention 4 is the same as that of the present invention 1. Invention 4 CPV
The chlorine content, the porosity, and the BET specific surface area of C are the same as those of the second invention, and the absorbance at 235 nm is the same as that of the third invention.

The chlorinated vinyl chloride-based resin according to the invention of claim 5 (hereinafter referred to as Invention 5) is a chlorinated vinyl chloride-based resin obtained by chlorinating a vinyl chloride-based resin. In particle surface analysis by electron spectrochemical analysis (ESCA), 1S of carbon atom and chlorine atom
The peak ratio (chlorine element peak × 2 / carbon element peak) in the binding energy value (eV) exceeds 0.6, and the chlorine content of the chlorinated vinyl chloride resin is 6%.
0 to 72% by weight, a porosity of 30 to 40% by volume measured at a pressure of 196 MPa by a mercury intrusion method, and a pore volume distribution of 0.001 to 0.1 μm in a pore volume distribution measured at a pressure of 0 to 196 MPa by a mercury intrusion method. The void volume is the total void volume
The absorbance (cell length 1 cm, measurement temperature 23 ° C.) of 2 to 15% by volume and 1 g / kg tetrahydrofuran solution is 0.2 or less at a wavelength of 235 nm.

The peak ratio in the ESCA analysis of the PVC of the fifth invention is the same as that of the first invention. Further, the chlorine content, porosity, and 0.001 to 0.
The void volume of 1 μm is the same as that of the third embodiment.

The absorbance of the CPVC of the fifth invention at a wavelength of 235 nm is limited to 0.2 or less. CPVC wavelength 23
When the absorbance at 5 nm is 0.2 or less, the thermal stability is particularly excellent.

The chlorinated vinyl chloride resin according to the invention (claim 6) is a chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin, wherein the vinyl chloride resin is In particle surface analysis by electron spectrochemical analysis (ESCA), 1S of carbon atom and chlorine atom
The peak ratio (chlorine element peak × 2 / carbon element peak) in the binding energy value (eV) exceeds 0.6, and the chlorine content of the chlorinated vinyl chloride resin is 6%.
The porosity measured at a pressure of 196 MPa by a mercury intrusion method is 30 to 40% by volume, the BET specific surface area is ² to 12 m ² / g, and the absorbance of a 1 g / kg tetrahydrofuran solution (cell length 1 cm, measurement temperature 23 ° C.) is 0.2 or less at a wavelength of 235 nm.

The peak ratio in the ESCA analysis of the PVC of the sixth invention is the same as that of the first invention. Further, the chlorine content, the porosity, and the BET specific surface area of the CPVC of the sixth invention are the same as those of the fourth invention, and the absorbance at a wavelength of 235 nm is the same as that of the fifth invention.

The method for producing a chlorinated vinyl chloride resin according to the invention of claim 7 (hereinafter referred to as Invention 7) is a method for producing a chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin. The vinyl chloride resin has a BET specific surface area of 1.3 to 8 m ² / g, and in particle surface analysis by electron spectrochemical analysis (ESCA), a 1S binding energy value (eV) of a carbon element and a chlorine element. The peak ratio (chlorine element peak × 2 / carbon element peak) at 0.
In addition, in the chlorination, liquid chlorine or gaseous chlorine is introduced into the reactor in a state where the vinyl chloride resin is suspended in an aqueous medium, and the reaction temperature is increased to 70%.
It is characterized in that the reaction is carried out in a temperature range of up to 135 ° C.

The PVC used in the present invention 7 is VCM
This is a resin obtained by polymerizing VCM alone or a mixture of VCM and another monomer copolymerizable with VCM by a known method. The monomer polymerizable with the VCN is not particularly limited,
For example, alkyl vinyl esters such as vinyl acetate; α-monoolefins such as ethylene and propylene; vinylidene chloride; styrene; These may be used alone or in combination of two or more.

The average degree of polymerization of the above PVC is not particularly limited, and those commonly used in the range of 400 to 3000 can be used.

BET ratio table of PVC used in the present invention 7
Area value is 1.3-8m^Two/ G, preferably
Is 1.5-5m^Two/ G. BET specific surface area
1.3m ^Two/ G is less than 0.1 in the PVC particles.
Chlorination becomes uniform because the number of micropores
No longer improves thermal stability,
Is slow. Conversely, the BET specific surface area value is 8m^Two/ G
If it exceeds, the thermal stability of PVC particles themselves before chlorination decreases.
Therefore, the workability of the obtained CPVC deteriorates.

The PVC used in the present invention 7 is ES
In the particle surface analysis by CA analysis, the peak ratio (chlorine element peak × 2 / carbon element peak) in the 1S bond energy value (eV) between the carbon element and the chlorine element is limited to a value exceeding 0.6, preferably 0. .7. When the peak ratio is 0.6 or less, it is considered that an additive such as a dispersant is adsorbed on the surface of the PVC particles.
A problem arises in the formability of the VC, and the thermal stability becomes poor. Among the PVCs having a peak ratio of more than 0.6, there are particles (skin-less PVC) having a small skin area on the surface of the PVC particles and exposing a fine structure (primary particles) inside the particles. When the energy ratio is the same, it is preferable to use skinless PVC.

The atomic abundance of the chemical structure of PVC is as follows:
The chlorine atom: carbon atom = 1: 2 (when the terminal structure and branching are not considered), and the peak ratio (chlorine element peak × 2 / carbon element peak) in the above 1S binding energy value (eV) is a value of 0 to 1. Becomes If the peak ratio is 0, PV
This means that the surface of the C particles is covered with a substance other than PVC and containing no chlorine. If the peak ratio is 1, the surface of the PVC particles is completely covered with only the PVC component. Means that.

PVC having a peak ratio at the above-mentioned BET specific surface area value and 1S binding energy value (eV)
Are, for example, polyvinyl acetate, higher fatty acid esters or the like having a high saponification degree (60 to 90 mol%) or a low saponification degree (20 to 60 mol%) as a dispersant, and an anionic emulsifier as an emulsifier. Alternatively, it can be obtained by adding a nonionic emulsifier or the like and conducting water suspension polymerization.

The shape and structure of the polymerization vessel (pressure-resistant autoclave) that can be used when polymerizing PVC in the present invention 7 are not particularly limited, and those generally used for polymerization of PVC may be used. it can. The stirring blade is not particularly limited, and includes, for example, those generally used such as a Faudler blade, a paddle blade, a turbine blade, a fan turbine blade, and a bull margin blade. It is preferably used, and the combination with a baffle is not particularly limited.

In the present invention 7, the method for chlorinating PVC is as follows.
In a state where VC is suspended in an aqueous medium, liquid chlorine or gaseous chlorine is introduced into the reactor, and a reaction temperature of 70 to 13 is applied.
This is a method in which a chlorination reaction is performed in a range of 5 ° C.

As the material of the chlorination reactor used in the present invention 7, in addition to a stainless steel reactor with a glass lining, a titanium reactor and the like can be used. In the present invention 7, chlorination is performed by introducing liquid chlorine or gaseous chlorine in a state where PVC is suspended in an aqueous medium, thereby introducing a chlorine source into the chlorination reactor. The introduction is efficient from the viewpoint of the process. For pressure adjustment during the reaction and for replenishment of chlorine with the progress of the chlorination reaction, gaseous chlorine other than liquid chlorine can be blown as appropriate.

As a method for preparing the above-mentioned PVC in a suspended state, it is preferable to use the resin on the cake which has been subjected to demonomerization treatment after polymerizing PVC, but the dried one is again suspended in an aqueous medium. Alternatively, a suspension obtained by removing substances that are not preferable for the chlorination reaction from the polymerization system may be used. The amount of the aqueous medium to be charged into the reactor is not particularly limited, but is generally 2 to 1 with respect to 1 weight of PVC.
It is preferable to charge 0 times (weight).

As a method of chlorinating in a suspended state as described above, there are a method of promoting the chlorination by exciting resin binding and chlorine by heat (hereinafter referred to as hot chlorination) and a method of irradiating light. (Hereinafter referred to as photochlorination), etc., but there is no particular limitation, and thermal chlorination is preferably used. When performing the thermal chlorination, the heating method is not particularly limited, and examples thereof include an external jacket method from the reactor wall, an internal jacket method, a steam blowing method, and the like. The scheme is effective. Further, light energy such as ultraviolet rays may be used in combination, but in this case,
A device that can irradiate ultraviolet light under high temperature and high pressure conditions is required.

The chlorine content of CPVC obtained in the chlorination step is preferably adjusted to be 60 to 72% by weight, more preferably 63 to 70% by weight. If the chlorine content is less than 60% by weight, the heat resistance may be poor. If the chlorine content is more than 72% by weight, the gelling performance may be deteriorated, which may be disadvantageous for forming a heat-resistant molded product. .

The reaction temperature of the chlorination according to the present invention 7 is 70
To 135 ° C, preferably 90 to 125 ° C. If the reaction temperature is lower than 70 ° C., the chlorination reaction rate is low, so that it is necessary to add a large amount of a reaction catalyst typified by a peroxide in order to advance the reaction. Stability becomes poor. Conversely, if the reaction temperature is 1
When the temperature exceeds 35 ° C., the resin is deteriorated by heat energy, and the obtained PVC is colored.

As chlorine used in the present invention 7, it is preferable to use chlorine after purging 5 to 10% by weight of cylinder chlorine as described in JP-A-6-32822. Further, the gauge pressure in the reactor is not particularly limited, but is preferably in the range of 0.3 to 2 MPa because the higher the chlorine pressure, the more easily chlorine permeates into the PVC particles.

The method for producing a chlorinated vinyl chloride resin according to the invention of claim 8 (hereinafter referred to as Invention 8) is characterized in that the BET specific surface area of the vinyl chloride resin is 1.5 to ⁵ m ² / g. This is a method for producing a chlorinated vinyl chloride resin.

According to a ninth aspect of the present invention, there is provided a method for producing a chlorinated vinyl chloride resin, wherein the peak ratio in the particle surface analysis of the vinyl chloride resin by ESCA analysis exceeds 0.7. The present invention 7 or 8 which is
Is a method for producing a chlorinated vinyl chloride resin.

The chlorinated vinyl chloride resin molded article according to the invention of claim 10 (hereinafter referred to as invention 10) is characterized in that the invention 1
A chlorinated vinyl chloride resin molded article obtained by molding any one of chlorinated vinyl chloride resins according to JIS,
Vicat softening temperature under a load of 9.8 N measured by a method in accordance with K 7206 is 145 ° C. or more.

In the present invention 10, the Vicat softening temperature is an index of the heat resistance of the chlorinated vinyl chloride resin molded product, and is limited to 145 ° C. or higher, and preferably 155 ° C. or higher. If the Vicat softening temperature is lower than 145 ° C., it is difficult to use a liquid or gas at a temperature of 100 ° C. or higher, which is a field represented by a hot water supply pipe that requires higher heat resistance than the current field of use. The upper limit of the Vicat softening temperature is preferably higher, but is preferably 185 ° C. or lower in consideration of the actual extrusion of a tubular molded body.

When molding the CPVC molded article of the present invention 10, it can be molded using commonly used compounding agents such as stabilizers, lubricants, modifiers, fillers, processing aids, pigments and the like. In molding the CPVC molded article, the molding machine is not particularly limited, and examples thereof include an extrusion molding machine, an injection molding machine, and a calender molding machine. The above CPVC
The mold for molding the molded body, the resin temperature, and the molding conditions are not particularly limited.

The chlorinated vinyl chloride resin molded article according to the invention of claim 11 (hereinafter referred to as invention 11) is the invention 1
A chlorinated vinyl chloride resin molded article obtained by molding any one of chlorinated vinyl chloride resins according to JIS,
Vicat softening temperature under a load of 9.8 N measured by a method in accordance with K 7206 is 145 ° C. or more, and is in accordance with JIS K
The Charpy impact value measured by a method based on 7111 is 10 kJ / m ² or more.

The Vicat softening temperature of the CPVC compact of the eleventh invention is the same as that of the tenth invention. In the present invention 11, the Charpy impact value measured by a method based on JIS K 7111 is 10 kJ / m ² or more. The Charpy impact value is an index of the impact strength of the molded product. If the Charpy impact value is 10 kJ / m ² or more, the Charpy impact value is 100 ° C.
It is preferable as a molded body through which the above liquid and gas flow. Further, the CPVC molded article of the present invention 11 is a CVC molded article of the present invention 1-6.
Molding is performed using PVC. Generally, when a highly chlorinated resin is used, the resulting molded article becomes brittle due to insufficient gelation during molding. For this reason, molding is performed by increasing the amount of the impact modifier added, but on the other hand, it also causes a reduction in heat resistance. Therefore, a preferable range is 10 to 60 kJ.
/ M ² , more preferably 15 to 50 kJ / m ² .

The chlorinated vinyl chloride resin molded article according to the invention of the twelfth aspect (hereinafter referred to as the twelfth aspect) is the first aspect of the invention.
A chlorinated vinyl chloride resin molded article obtained by molding any one of chlorinated vinyl chloride resins according to JIS,
Vicat softening temperature under a load of 9.8 N measured by a method in accordance with K 7206 is 145 ° C. or more, and is in accordance with JIS K
The Charpy impact value measured by a method based on 7111 is 20 kJ / m ² or more.

The Vicat softening temperature of the CPVC molded article of the twelfth invention is the same as that of the tenth invention. CP of Invention 12
The VC shaped article has a Charpy impact value of 20 kJ / m ² or more, and is suitably used when higher heat resistance and impact strength are required.

The chlorinated vinyl chloride resin pipe according to the invention of the thirteenth aspect (hereinafter referred to as the thirteenth invention) is the same as the first to sixth inventions.
A chlorinated vinyl chloride-based resin pipe obtained by molding any chlorinated vinyl chloride-based resin.
A Vicat softening temperature under a load of 9.8 N measured by a method in accordance with J.06 is 120 ° C. or higher, and a water absorption rate after performing a 90 ° C. hot water immersion test for 60 days is 1.5% or less.
In a long-term internal pressure creep test at 90 ° C. in accordance with STM D 2837, a breaking stress after a breaking time of 1000 hours is 4.5 MPa or more.

The Vicat softening temperature of the CPVC tube of the thirteenth invention is 120 ° C. or higher. Vicat softening temperature of 120
If it is lower than ℃, it is difficult to use as a hot water supply pipe for flowing hot water of 80 to 90 ℃. The upper limit of the Vicat softening temperature is preferably higher, but is preferably 185 ° C. or lower in consideration of the actual extrusion of a tubular molded body.

The CPVC pipe of the thirteenth invention has a water absorption of 1.5% or less, more preferably 1.0% or less, after performing a hot water immersion test at 90 ° C. for 60 days. When the water absorption exceeds 1.5%, expansion and destruction due to water absorption are likely to occur.

The CPVC tube of the thirteenth invention is an ASTM D
In a long-term internal pressure creep test at 90 ° C. in accordance with No. 2837, the breaking stress after a lapse of 1000 hours was 4.
It is at least 5 MPa, preferably at least 6.0 MPa, more preferably at least 7.0 MPa. If the fracture stress is less than 4.5 MPa, it is difficult to use the hot water supply pipe for a long time.

When molding the CPVC tube of the thirteenth invention, it can be molded using commonly used compounding agents such as stabilizers, lubricants, modifiers, fillers, processing aids, pigments and the like. In the molding of the CPVC pipe, the molding machine is not particularly limited, and examples thereof include a single-screw extruder, a twin-screw parallel directional extruder, a twin-screw conical extruder, and a twin-screw extruder. . The mold, resin temperature, and molding conditions for molding the CPVC pipe are not particularly limited.

The chlorinated vinyl chloride resin tube according to the invention of the fourteenth aspect (hereinafter referred to as the invention 14) is the same as that of the inventions 1-6.
A chlorinated vinyl chloride-based resin pipe obtained by molding any chlorinated vinyl chloride-based resin.
A Vicat softening temperature under a load of 9.8 N measured by a method in accordance with J.06 is 120 ° C. or higher, and a water absorption rate after performing a 90 ° C. hot water immersion test for 60 days is 1.5% or less.
In a long-term internal pressure creep test at 90 ° C. in accordance with STM D 2837, a breaking stress after a lapse of 1000 hours is 4.5 MPa or more, and a surface roughness Rmax is 5.0 μm or less.

The Vicat softening temperature, water absorption and breaking stress of the CPVC pipe of the fourteenth invention are the same as those of the thirteenth invention. The surface roughness Rmax of the CPVC tube according to Invention 14 is 5.0 μm.
m, preferably 1.5 μm, especially 0.1 μm.
It is preferably 5 μm or less. When Rmax exceeds 5.0 μm, stagnation occurs due to unevenness, and impurities are accumulated in the stagnation portion, and bacteria are generated, so that it is difficult to use the tube as a tube. When the surface roughness Rmax is 0.5 μm or less, it can be used for ultrapure water piping for plants. The blending and molding conditions for molding the CPVC pipe of the present invention 14 are the same as those of the present invention 13.

The chlorinated vinyl chloride-based resin pipe according to the thirteenth or fourteenth aspect of the present invention is characterized in that the chlorinated vinyl chloride-based resin pipe according to the invention of claim 15 is a resin pipe for hot water supply. It is.

The lining pipe according to the sixteenth aspect of the present invention (hereinafter referred to as the sixteenth aspect) is provided inside the metal pipe.
Alternatively, 14 chlorinated vinyl chloride resin tubes are lined.

The metal pipe used for the lining pipe of the present invention 16 is not particularly limited, and a steel pipe is preferably used. In the lining pipe, the metal pipe and the present invention 13 or 1
The method for bonding the CPVC pipe No. 4 is not particularly limited, and a method based on diameter reduction of a steel pipe is suitably used. Further, the adhesive for bonding the metal pipe and the CPVC pipe, bonding conditions, and the like are not particularly limited.

In the CPVC of the present invention, first, a characteristic is given to the particle structure of the CPVC. That is, by defining the internal porous state, the gelling property at the time of molding is developed. Next, high heat stability is expressed by defining the amount of heterogeneous structure in the CPVC molecular chain. Thus, according to the present invention, a resin having both high heat stability and gelling property is provided.

In the production method of the present invention, first, a characteristic is given to the particle structure of PVC. That is, by defining the surface state and the internal porous state, the gelling property at the time of molding is developed. Next, by defining the reaction temperature,
Develop high thermal stability. The development of high thermal stability due to this high-temperature reaction is such that oxidation (formation of a heterogeneous structure represented by a carbonyl group) during the chlorination reaction is less likely to occur at higher temperatures (the higher the temperature, the more the reaction equilibrium moves in a direction to suppress the formation). It is based on that. Thus, according to the present invention, it is possible to produce a resin having both high thermal stability and gelling property.

The CPVC molded article of the present invention is
By using VC, the gel is sufficiently gelled at the time of molding, and heat resistance and impact strength are exhibited. In this way, it is possible to produce a molded article having excellent heat resistance and impact strength.

The CPVC tube of the present invention is the same as the CPVC tube of the present invention.
By using, a gel is sufficiently formed at the time of molding, and physical properties such as heat resistance are exhibited. In this way, it is possible to manufacture a tube having excellent high-temperature creep performance and the like.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Example 1) [Preparation of PVC] A polymerization vessel having an inner volume of 100 liter (withstand pressure)
50 kg of deionized water and vinyl chloride
Monomer, partially saponified polyvinyl acetate (average saponification
Degree 72 mol% and degree of polymerization 700) 400 ppm, sorby
1600 ppm of tantalum monolaurate (HLB8.6),
Lauric acid 1500 ppm, polyacrylamide (20
At 0.1325 MPa and a 0.1% by weight aqueous solution.
Kufields viscosity is 51 mPa · s) 100 ppm, and
And t-butyl peroxy neodecanoate 500 ppm
Was introduced. Next, the inside of the polymerization vessel was degassed to 6 kPa.
After that, charge 33 kg of vinyl chloride monomer and start stirring.
Was. The polymerization was started by raising the temperature of the polymerization vessel to 57 ° C.
This temperature was maintained until completion. 90% polymerization conversion
When the reaction is completed, the reaction is terminated and the unreacted monomer in the polymerization vessel is recovered.
After that, the polymer is taken out of the system in slurry form, dehydrated and dried.
After drying, PVC was obtained. BET specific surface area of the obtained PVC
Is 3.7m ^Two/ G. Also, the extent of the skin layer
The ESCA analysis value for was 0.80. Note that B
The measurement of the ET specific surface area and the ESCA analysis is performed by the following method.
More.

[Preparation of CPVC] 150 k of deionized water was placed in a 300-liter glass-lined pressure-resistant reaction vessel.
g, and 40 kg of the PVC obtained above, and stirred.
Is dispersed in water, the internal air is sucked by a vacuum pump,
The pressure was reduced until the gauge pressure became -78.4 kPa. The pressure was returned with nitrogen gas (returned until the gauge pressure became 0), and the inside of the reaction tank was removed by suction with a vacuum pump again. During this time, the heated oil was passed through the jacket to heat the inside of the reactor. When the temperature in the reaction tank reached 90 ° C., the supply of chlorine gas was started, and the reaction was allowed to proceed at a constant temperature of 110 ° C. Calculate the chlorine content from the concentration of hydrogen chloride generated in the reaction tank, and when the chlorine content is 63% by weight, the concentration is 100 pp.
The reaction was continued while continuously adding 0.5 kg / hr of aqueous hydrogen peroxide. When the chlorine content reached 66.5% by weight, the supply of chlorine gas was stopped, and the chlorination reaction was terminated. The amount of hydrogen peroxide added during the reaction was 4 ppm based on the charged resin amount. Furthermore, nitrogen gas was blown into the reaction tank to remove unreacted chlorine, and the obtained resin was washed with water, dehydrated, and dried to obtain a powdery CPVC. Obtained C
The chlorine content of PVC is 66.5% by weight, and the porosity is 34.
6% by volume, specific surface area value is 6.4 m ^{2 /} g, 0.001 to
Void volume in the range of 0.1 μm (hereinafter referred to as void volume)
Was 7.8% by volume.

(Example 2) Preparation of PVC was carried out in the same manner as in Example 1. [Preparation of CPVC] 150 kg of deionized water and P obtained above were placed in a glass-lined reaction vessel having an internal volume of 300 liters.
Add 40 kg of VC, stir to disperse PVC in water, suck the internal air with a vacuum pump, and set the gauge pressure to -7.
The pressure was reduced to 8.4 kPa. The pressure was returned with nitrogen gas, and the inside of the tank was replaced with nitrogen gas. During this time, the heated oil was passed through the jacket to heat the inside of the reactor. When the temperature inside the reaction tank reached 70 ° C., the supply of chlorine gas was started, and the reaction was allowed to proceed while irradiating the inside of the tank with ultraviolet rays using a mercury lamp. The chlorine content was calculated from the concentration of hydrogen chloride generated in the reaction tank. When the chlorine content reached 66.5% by weight, the supply of chlorine gas was stopped, and the chlorination reaction was terminated.
Furthermore, nitrogen gas was blown into the reaction tank to remove unreacted chlorine, and the obtained resin was washed with water, dehydrated, and dried to obtain a powdery CPVC. The chlorine content of the obtained CPVC is 6
6.5% by weight, porosity was 35.2% by volume, specific surface area was 6.6 m ² / g, and void volume was 8.1% by volume.

Example 3 Preparation of PVC was carried out in the same manner as in Example 1. [Preparation of CPVC] 150 kg of deionized water and 40 kg of the above-obtained PVC were placed in a 300-liter glass-lined pressure-resistant reaction vessel having an internal volume of 300 liters, and stirred to disperse the PVC in water. Gauge pressure is-
The pressure was reduced to 78.4 kPa. The pressure was returned with nitrogen gas, and the pressure in the reaction tank was removed again by suction with a vacuum pump to remove oxygen. During this time, the heated oil was passed through the jacket to heat the inside of the reactor. When the temperature in the reaction tank reached 85 ° C., the supply of chlorine gas was started, and the reaction was allowed to proceed at a constant temperature of 90 ° C. Calculate the chlorine content from the concentration of hydrogen chloride generated in the reaction tank, and when the chlorine content is 62% by weight, the concentration is 100 pp.
The reaction was continued while continuously adding 0.5 kg / hr of aqueous hydrogen peroxide. When the chlorine content reached 66.5% by weight, the supply of chlorine gas was stopped, and the chlorination reaction was terminated. The amount of hydrogen peroxide added during the reaction was 8 ppm based on the charged resin amount. The porosity of the obtained CPVC is 3
5.0 volume%, the specific surface area value was 6.6 m ² / g, and the void volume was 8.0 volume%.

Example 4 Preparation of PVC was carried out in the same manner as in Example 1. Preparation of CPVC requires a reaction temperature of 130
The procedure was performed in the same manner as in Example 1 except that the temperature was changed to ° C., and hydrogen peroxide was not added. Furthermore, nitrogen gas was blown into the reaction tank to remove unreacted chlorine, and the obtained resin was washed with water, dehydrated, and dried to obtain a powdery CPVC.
The chlorine content of the obtained CPVC was 66.5% by weight, the porosity was 33.9% by volume, the specific surface area value was 6.1 m ² / g, and the void volume was 7.6% by volume.

Example 5 Preparation of PVC was performed in the same manner as in Example 1 except that the partially saponified polyvinyl acetate was changed to 550 ppm. Preparation of CPVC was performed in the same manner as in Example 1. The porosity of the obtained CPVC is 33.8% by volume,
Specific surface area value is 5.2 m ² / g, void volume is 6.3% by volume
Met.

(Example 6) Preparation of PVC was carried out in the same manner as in Example 1. Preparation of CPVC was carried out in the same manner as in Example 1, except that the chlorine content of CPVC was 64.0% by weight, and hydrogen peroxide was not added.
The porosity of the obtained CPVC was 34.1% by volume, the specific surface area value was 6.3 m ² / g, and the void volume was 7.6% by volume.

(Example 7) Preparation of PVC was carried out in the same manner as in Example 1. Preparation of CPVC was carried out in the same manner as in Example 1, except that the chlorine content of CPVC was 70.0% by weight. The amount of hydrogen peroxide added was 10 ppm based on the charged resin amount. The porosity of the obtained CPVC was 35.3% by volume, the specific surface area was 6.7 m ² / g, and the void volume was 8.1% by volume.

(Comparative Example 1) [Preparation of PVC] In a polymerization vessel (pressure-resistant autoclave) having an internal volume of 100 liters, 50 kg of deionized water and a partially saponified polyvinyl acetate (average degree of saponification) with respect to a vinyl chloride monomer were used. After 1300 ppm of 72 mol% and a degree of polymerization of 750) were added as a suspending dispersant, 550 ppm of t-butylperoxy neodecanoate was added. Then, 4
After degassing to 5mmHg, vinyl chloride monomer 33kg
And stirring was started. The polymerization was started by raising the temperature of the polymerization vessel to 57 ° C., and this temperature was maintained until the polymerization reaction was completed. When the polymerization conversion reached 90%, the reaction was terminated. After the unreacted monomer in the polymerization vessel was recovered, the polymer was taken out of the system in the form of a slurry, and dehydrated and dried to obtain PVC. P obtained
The BET specific surface area of VC was 0.7 m ² / g. The ESCA analysis value indicating the degree of the presence of the skin layer is 0.1.
20. The BET specific surface area and ESCA
The analysis was measured by the following method.

The preparation of CPVC was carried out as in Example 1. The porosity of the obtained CPVC was 27.3% by volume, the specific surface area was 1.8 m ² / g, and the void volume was 1.1% by volume.

(Comparative Example 2) Preparation of PVC was carried out in the same manner as in Comparative Example 1. Preparation of CPVC was carried out as in Example 2. The porosity of the obtained CPVC was 27.9% by volume, the specific surface area was 2.0 m ² / g, and the void volume was 1.4% by volume.

(Comparative Example 3) Preparation of PVC was carried out in the same manner as in Example 1. Preparation of CPVC requires a reaction temperature of 140
The procedure was performed in the same manner as in Example 1 except that the temperature was changed to ° C., and hydrogen peroxide was not added. The porosity of the obtained CPVC is 28.8% by volume, and the specific surface area value is 1.9 m ² /
g, the void volume was 1.3% by volume.

(Comparative Example 4) Preparation of PVC was carried out in the same manner as in Example 1. CPVC was prepared in the same manner as in Example 1 except that the chlorine content of CPVC was 73.0% by weight. The amount of hydrogen peroxide added was 40 ppm based on the charged resin amount. The porosity of the obtained CPVC was 36.8% by volume, the specific surface area value was 10.0 m ² / g, and the void volume was 12.1% by volume.

The performance of the CPVC obtained in Examples 1 to 7 and Comparative Examples 1 to 4 was evaluated, and the results are shown in Table 1.

[0085]

[Table 1]

(Example 8) Both the preparation of PVC and the preparation of CPVC were carried out in the same manner as in Example 1. Obtained CPVC
Was dissolved in tetrahydrofuran to prepare a solution having a concentration of 1 g / kg. When the absorbance of this solution at a wavelength of 235 nm was measured at a cell length of 1 cm and a measurement temperature of 23 ° C.,
0.13.

(Example 9) Preparation of PVC was carried out in the same manner as in Example 1. Preparation of CPVC was carried out as in Example 2. The obtained CPVC was dissolved in tetrahydrofuran to prepare a solution having a concentration of 1 g / kg. Of this solution,
When the absorbance at a wavelength of 235 nm was measured at a cell length of 1 cm and a measurement temperature of 23 ° C., it was 0.70.

Example 10 Preparation of PVC was performed according to Example 1.
Was carried out in the same manner as Preparation of CPVC was carried out as in Example 3. The obtained CPVC was dissolved in tetrahydrofuran to prepare a solution having a concentration of 1 g / kg. When the absorbance of this solution at a wavelength of 235 nm was measured at a cell length of 1 cm and a measurement temperature of 23 ° C., it was 0.12.

(Example 11) Preparation of PVC was performed in the same manner as in Example 1.
Was carried out in the same manner as Preparation of CPVC was carried out as in Example 4. The obtained CPVC was dissolved in tetrahydrofuran to prepare a solution having a concentration of 1 g / kg. When the absorbance of this solution at a wavelength of 235 nm was measured at a cell length of 1 cm and a measurement temperature of 23 ° C., it was 0.32.

(Example 12) Both the preparation of PVC and the preparation of CPVC were carried out in the same manner as in Example 5. Obtained CPV
C was dissolved in tetrahydrofuran to prepare a solution having a concentration of 1 g / kg. When the absorbance of this solution at a wavelength of 235 nm was measured at a cell length of 1 cm and a measurement temperature of 23 ° C.,
0.14.

Example 13 Preparation of PVC was performed according to Example 1.
Was carried out in the same manner as Preparation of CPVC was carried out as in Example 6. The obtained CPVC was dissolved in tetrahydrofuran to prepare a solution having a concentration of 1 g / kg. When the absorbance of this solution at a wavelength of 235 nm was measured at a cell length of 1 cm and a measurement temperature of 23 ° C., it was 0.10.

Example 14 Preparation of PVC was performed according to Example 1.
Was carried out in the same manner as Preparation of CPVC was carried out as in Example 7. The obtained CPVC was dissolved in tetrahydrofuran to prepare a solution having a concentration of 1 g / kg. When the absorbance of this solution at a wavelength of 235 nm was measured at a cell length of 1 cm and a measurement temperature of 23 ° C., it was 0.29.

Comparative Example 5 Preparation of PVC and CPVC were performed in the same manner as in Comparative Example 1. Obtained CPVC
Was dissolved in tetrahydrofuran to prepare a solution having a concentration of 1 g / kg. When the absorbance of this solution at a wavelength of 235 nm was measured at a cell length of 1 cm and a measurement temperature of 23 ° C.,
0.27.

(Comparative Example 6) Preparation of PVC was carried out in the same manner as in Comparative Example 1. Preparation of CPVC was performed in the same manner as in Comparative Example 2. The obtained CPVC was dissolved in tetrahydrofuran to prepare a solution having a concentration of 1 g / kg. Of this solution,
When the absorbance at a wavelength of 235 nm was measured at a cell length of 1 cm and a measurement temperature of 23 ° C., it was 0.85.

(Comparative Example 7) Preparation of PVC was carried out in the same manner as in Example 1. [Preparation of CPVC] 150 kg of deionized water and 40 kg of PVC obtained above were put into a pressure-resistant reaction vessel made of glass lining having an internal volume of 300 liters, and stirred to disperse the PVC in water. Gauge pressure is-
The pressure was reduced to 78.4 kPa. The pressure was returned with nitrogen gas, and the pressure in the reaction tank was removed again by suction with a vacuum pump to remove oxygen. During this time, the heated oil was passed through the jacket to heat the inside of the reactor. When the temperature in the reaction tank reached 60 ° C., the supply of chlorine gas was started, and the reaction was allowed to proceed at a constant temperature of 65 ° C. The chlorine content was calculated from the concentration of hydrogen chloride generated in the reaction tank, and when the chlorine content was 63% by weight, the concentration was 500 pp.
The reaction was continued while continuously adding 0.5 kg / hr of aqueous hydrogen peroxide. When the chlorine content reached 66.5% by weight, the supply of chlorine gas was stopped, and the chlorination reaction was terminated. The amount of hydrogen peroxide added during the reaction was 500 ppm based on the charged resin amount. Furthermore, nitrogen gas was blown into the reaction tank to remove unreacted chlorine, and the obtained resin was washed with water, dehydrated, and dried to obtain a powdery CPVC. The chlorine content of the obtained CPVC was 66.5% by weight. The obtained CPVC was dissolved in tetrahydrofuran and the concentration was 1
g / kg of solution was prepared. 235 n wavelength of this solution
When the absorbance at m was measured at a cell length of 1 cm and a measurement temperature of 23 ° C., it was 1.32. The porosity of this CPVC was 35.9% by volume, and the specific surface area was 6.9 m 2 /
g, the void volume was 8.3% by volume.

Comparative Example 8 Preparation of PVC was carried out in the same manner as in Example 1. The preparation of CPVC requires a reaction temperature of 60 ° C.
Example 2 was carried out in the same manner as in Example 2, except that The obtained CPVC was dissolved in tetrahydrofuran, and the concentration was 1 g / k.
g of solution was prepared. When the absorbance of this solution at a wavelength of 235 nm was measured at a cell length of 1 cm and a measurement temperature of 23 ° C., it was 0.92. The CPVC had a porosity of 36.0% by volume, a specific surface area of 7.0 m @ 2 / g, and a void volume of 8.5% by volume.

(Comparative Example 9) Preparation of PVC was carried out in the same manner as in Example 1. Preparation of CPVC was performed in the same manner as in Comparative Example 3. The obtained CPVC was dissolved in tetrahydrofuran to prepare a solution having a concentration of 1 g / kg. Of this solution,
When the absorbance at a wavelength of 235 nm was measured at a cell length of 1 cm and a measurement temperature of 23 ° C., it was 0.41.

Comparative Example 10 Preparation of PVC was performed in the same manner as in Example 1.
Was carried out in the same manner as Preparation of CPVC was performed in the same manner as in Comparative Example 4. The obtained CPVC was dissolved in tetrahydrofuran to prepare a solution having a concentration of 1 g / kg. The absorbance of this solution at a wavelength of 235 nm was 0.52 when measured at a cell length of 1 cm and a measurement temperature of 23 ° C.

Examples 8 to 14 and Comparative Examples 5 to 10
The performance evaluation was performed on the CPVC obtained in Table 2, and the results are shown in Table 2.

[0100]

[Table 2]

Example 15 Preparation of PVC was performed according to Example 1.
Was carried out in the same manner as CPVC was prepared in the same manner as in Example 1, except that the final chlorine content was 70.5% by weight.

[Blending] To 100 parts by weight (phr) of the CPVC obtained above, various additives shown in the blending 1 of Table 3 were added, and heated and mixed with a Henschel mixer.

[0103]

[Table 3]

[Molding] The above powder mixture was molded under the following extrusion conditions to obtain a tubular molded body having a diameter of 20 mm.・ Extruder: SLM50 (Two-axis different direction conical extruder, manufactured by Nagata Seisakusho Co., Ltd.) ・ Die: Die for pipe (outer radius of outlet: 11.66 m)
m, inner radius of outlet portion: 9.4 mm, chromium plating on resin flowing surface, Rmax = 5 μm, Ra = 0.1 μm (average of four locations in the circumferential direction of outlet portion, three bridges) ・ Amount of extrusion: 25 to 30 kg / hr ・ Resin Temperature: 215 to 217 ° C ・ Rotation speed: 20 to 30rpm ・ Barrel temperature: 185 to 210 ° C ・ Mold temperature: 200 to 215 ° C

Example 16 Preparation of PVC was performed according to Example 1.
The operation was performed in the same manner as in Example 5. Preparation of CPVC is described in Example 1.
5 and the reaction temperature was 120 ° C., and hydrogen peroxide was added in the same manner as in Example 5 except that the chlorine content was 65% by weight. The compounding and molding were performed in the same manner as in Example 15.

(Example 17) Preparation of PVC was performed in the same manner as in Example 1.
The operation was performed in the same manner as in Example 5. Preparation of CPVC is described in Example 1.
And the final chlorine content was changed to 71.5% by weight. The compounding and molding were performed in the same manner as in Example 15.

(Comparative Example 11) Preparation of PVC was performed in the same manner as in Example 1.
The operation was performed in the same manner as in Example 5. Preparation of CPVC is described in Example 1.
The reaction was carried out in the same manner except that the reaction temperature was 140 ° C. and the final chlorine content was 69.0% by weight. The compounding and molding were performed in the same manner as in Example 15.

For the CPVC obtained in Examples 15 to 17 and Comparative Example 11, the chlorine content, porosity, void volume, BET specific surface area, ESC
The A analysis value was measured. Table 4 shows the results of measuring the Vicat softening point of the tubular molded body by the following measurement method.

[0109]

[Table 4]

(Example 18) Preparation of PVC was performed in the same manner as in Example 1.
The operation was performed in the same manner as in Example 5. Preparation of CPVC is described in Example 1.
The operation was performed in the same manner as in Example 5. The compounding and molding were performed in the same manner as in Example 15.

(Example 19) Preparation of PVC was performed according to Example 1.
The operation was performed in the same manner as in Example 5. Preparation of CPVC is described in Example 1.
6 was carried out in the same manner. The compounding and molding were performed in the same manner as in Example 15.

(Example 20) Preparation of PVC was performed in the same manner as in Example 1.
The operation was performed in the same manner as in Example 5. Preparation of CPVC is described in Example 1.
7 was carried out in the same manner. The compounding and molding were performed in the same manner as in Example 15.

Comparative Example 12 Preparation of PVC was performed according to Comparative Example 1.
It carried out similarly to. Preparation of CPVC is described in Example 15
It carried out similarly to. The compounding and molding were performed in the same manner as in Example 15.

(Comparative Example 13) Preparation of PVC was performed in the same manner as in Example 1.
The operation was performed in the same manner as in Example 5. Preparation of CPVC is described in Example 1.
The reaction was carried out in the same manner except that the reaction temperature was 140 ° C. and the final chlorine content was 70.5% by weight. The compounding and molding were performed in the same manner as in Example 15.

Comparative Example 14 Preparation of PVC was performed according to Example 1.
The operation was performed in the same manner as in Example 5. Preparation of CPVC was performed according to Comparative Example 1.
The procedure was performed in the same manner as in Example 1. The compounding and molding were performed in the same manner as in Example 15.

Examples 18 to 20 and Comparative Examples 12 to
About the CPVC obtained in 14, a chlorine content, a porosity, a void volume, a BET specific surface area,
ESCA analysis values were measured. Table 5 shows the results of measuring the Vicat softening point and the Charpy impact value of the tubular molded body by the following measurement methods.

[0117]

[Table 5]

(Example 21) Preparation of PVC was performed in the same manner as in Example 1.
The operation was performed in the same manner as in Example 5. Preparation of CPVC is described in Example 1.
7 was carried out in the same manner. The compounding | mixing added the various compounding agents shown to the compounding 2 of Table 3, and heat-mixed with the Henschel mixer. The molding was performed in the same manner as in Example 15.

Example 22 Preparation of PVC was performed according to Example 1.
The operation was performed in the same manner as in Example 5. Preparation of CPVC is described in Example 1.
6, except that the final chlorine content was 71.5% by weight. The compounding and molding were performed in the same manner as in Example 21.

Comparative Example 15 Preparation of PVC was performed according to Comparative Example 1.
It carried out similarly to. Preparation of CPVC is described in Example 17
It carried out similarly to. Compounding and molding were performed in the same manner as in Example 21.

(Comparative Example 16) Preparation of PVC was performed in the same manner as in Example 1.
The operation was performed in the same manner as in Example 5. Preparation of CPVC was performed according to Comparative Example 1.
3, except that the final chlorine content was 71.5% by weight. The compounding and molding were performed in the same manner as in Example 21.

(Comparative Example 17) Preparation of PVC was performed in the same manner as in Example 1.
The operation was performed in the same manner as in Example 5. Preparation of CPVC was performed according to Comparative Example 1.
The procedure was performed in the same manner as in Example 1. The compounding and molding were performed in the same manner as in Example 21.

Examples 21 and 22 and Comparative Examples 15 to
17, the chlorine content, the porosity, the void volume, the BET specific surface area,
ESCA analysis values were measured. Table 6 shows the results of measuring the Vicat softening point and the Charpy impact value of the tubular molded body by the following measuring methods.

[0124]

[Table 6]

(Example 23) [Preparation of PVC] In a polymerization vessel (pressure-resistant autoclave) having an internal volume of 100 liters, 50 kg of deionized water and a partially saponified polyvinyl acetate (average degree of saponification) with respect to a vinyl chloride monomer were used. 72 mol% and degree of polymerization 700) 400 ppm, sorbitan monolaurate (HLB 8.6) 1600 ppm,
Lauric acid 1500 ppm, polyacrylamide (20
Brookfield viscosity of a 0.1% by weight aqueous solution at 101325 MPa is 51 mPa · s) 100 ppm and t-butyl peroxy neodecanoate 500 ppm
Was introduced. Next, after degassing the inside of the polymerization vessel to 6 kPa, 33 kg of a vinyl chloride monomer was charged and stirring was started. The polymerization was started by raising the temperature of the polymerization vessel to 57 ° C., and this temperature was maintained until the polymerization reaction was completed. When the polymerization conversion reached 90%, the reaction was terminated, and the unreacted monomer in the polymerization vessel was recovered. Then, the polymer was taken out of the system in the form of slurry, and dehydrated and dried to obtain PVC. The BET specific surface area of the obtained PVC was 3.7 m 2 / g. The ESCA analysis value indicating the degree of the existence of the skin layer was 0.80. Note that B
The measurement of the ET specific surface area and the ESCA analysis were performed by the following methods.

[Preparation of CPVC] 150 k of deionized water was placed in a 300-liter glass-lined pressure-resistant reaction vessel.
g and 40 kg of the PVC obtained above,
C was dispersed in water, the internal air was sucked by a vacuum pump, and the pressure was reduced until the gauge pressure became -78.4 kPa.
The pressure was returned with nitrogen gas, and the pressure in the reaction tank was removed again by suction with a vacuum pump to remove oxygen. During this time, the heated oil was passed through the jacket to heat the inside of the reactor. When the temperature in the reaction tank reached 90 ° C., the supply of chlorine gas was started, and
The reaction was allowed to proceed at a constant temperature. The chlorine content was calculated from the concentration of hydrogen chloride generated in the reaction tank, and when the chlorine content was 63% by weight, 0.5 kg / h of hydrogen peroxide having a concentration of 100 ppm was added.
The reaction was continued while continuously adding at r. Chlorine content is 6
When it reaches 6.5% by weight, the supply of chlorine gas is stopped,
The chlorination reaction was completed. The amount of hydrogen peroxide added during the reaction was 4 ppm based on the charged resin amount. Further, nitrogen gas is blown into the reaction tank to remove unreacted chlorine, and the obtained resin is washed with water, dehydrated and dried to obtain a powdery CPVC.
I got The chlorine content of the obtained CPVC is 66.5% by weight.
%, Porosity is 34.6% by volume, specific surface area value is 6.4m2
/ G, the void volume was 7.8% by volume, and the ESCA analysis value was 0.71.

[Formulation] 100 parts by weight of the above CPVC (ph
Various compounding agents shown in Table 7 were added to r), and mixed by heating with a Henschel mixer.

[0128]

[Table 7]

[Molding] Using the above blended powder, molding was carried out under the following extrusion conditions to obtain a tube having a diameter of 20 mm.・ Extruder: SLM50 (Two-axis different direction conical extruder, manufactured by Nagata Seisakusho Co., Ltd.) ・ Die: Die for pipe (outer radius of outlet: 11.66 m)
m, outlet inner radius: 9.4 mm, chromium plating on the resin flow surface, Rmax = 5 μm, Ra = 0.1 μm (average of four locations in the circumferential direction of the outlet), three bridges) ・ Extrusion: 25-30 kg / hr ・ Resin Temperature: 205 to 207 ° C ・ Rotation speed: 20 to 30 rpm ・ Barrel temperature: 185 to 210 ° C ・ Mold temperature: 200 to 215 ° C

Example 24 Preparation of PVC was carried out in the same manner as in Example 23 except that the partially saponified polyvinyl acetate was changed to 550 ppm. BE of the obtained PVC
The T specific surface area was 2.5 m @ 2 / g. The ESCA analysis value indicating the extent of the presence of the skin layer was 0.63. The BET specific surface area and ESCA analysis were measured by the following methods. Preparation of CPVC was performed in the same manner as in Example 23. The porosity of the obtained CPVC was 33.8% by volume, the specific surface area value was 5.2 m 2 / g, the void volume was 6.3% by volume, and the ESCA analysis value was 0.60. The compounding and molding were performed in the same manner as in Example 23.

(Comparative Example 18) [Preparation of PVC] In a polymerization vessel (pressure-resistant autoclave) having an inner volume of 100 liters, 50 kg of deionized water and a partially saponified polyvinyl acetate (average saponification degree) with respect to a vinyl chloride monomer were used. After 1300 ppm of 72 mol% and a degree of polymerization of 750) were added as a suspending dispersant, 550 ppm of t-butylperoxy neodecanoate was added. Then, 4
After degassing to 5mmHg, vinyl chloride monomer 33kg
And stirring was started. The polymerization was started by raising the temperature of the polymerization vessel to 57 ° C., and this temperature was maintained until the polymerization reaction was completed. When the polymerization conversion reached 90%, the reaction was terminated, and the unreacted monomer in the polymerization vessel was recovered. Then, the polymer was taken out of the system in the form of slurry, and dehydrated and dried to obtain PVC. P obtained
The BET specific surface area of VC was 0.7 m @ 2 / g. The ESCA analysis value indicating the degree of the presence of the skin layer is 0.1.
20. The BET specific surface area and ESCA
The analysis was measured by the following method.

The preparation of CPVC was carried out as in Example 23. The porosity of the obtained CPVC was 27.3% by volume,
Specific surface area value is 1.8 m 2 / g, void volume is 1.1% by volume
, And ESCA analysis were 0.21. The compounding and molding were performed in the same manner as in Example 23.

(Comparative Example 19) Preparation of PVC was performed in the same manner as in Example 2.
The same operation as in Example 3 was performed. CPVC was prepared in the same manner as in Example 23 except that the final chlorine content was 64.0% by weight. The porosity of the obtained CPVC is 34.2 volumes
%, Specific surface area value was 5.8 m @ 2 / g, void volume was 7.5 volume%, and ESCA analysis value was 0.70. The compounding and molding were performed in the same manner as in Example 23.

(Comparative Example 20) Preparation of PVC was performed according to Comparative Example 1.
8 was performed. CPVC was prepared in the same manner as in Example 23 except that the final chlorine content was 68.5% by weight. The porosity of the obtained CPVC is 29.1.
%, Specific surface area 4.8 m @ 2 / g, void volume 4.
3% by volume, ESCA analysis value was 0.20. Formulation
The molding was performed in the same manner as in Example 23.

Examples 23 and 24 and Comparative Examples 18 to
About the CPVC obtained in No. 20, a chlorine content, a porosity, a void volume, a BET specific surface area,
ESCA analysis values were measured. Table 8 shows the results of measuring the water absorption, the Vicat softening temperature, the internal pressure creep test (1000-hour fracture stress), and the surface roughness Rmax of the tubular molded body by the following measurement methods.

[0136]

[Table 8]

[Evaluation Method] (Evaluation of PVC) The above Examples 1 to 14 and Comparative Examples 1 to 1
Of BET specific surface area value of PVC used at 0 and ESC
The method of A analysis is as follows. (1) Measurement of BET specific surface area value About 2 g of a measurement sample is put into a sample tube, and 7
After degassing the sample for 3 hours at 0 ° C., the sample weight was measured accurately. The sample after the pretreatment was attached to a measuring section (40 ° C. constant temperature bath) to start measurement. After the measurement, a BET plot was performed from the data on the adsorption side of the adsorption isotherm to calculate the specific surface area. In addition, a specific surface area measuring device “BELSORP28SA” (manufactured by Nippon Bell Co., Ltd.) was used as a measuring device, and nitrogen gas was used as a measuring gas.

(2) ESCA Analysis The surface of the PVC particles was analyzed by ESCA (Electron Sp
electroscopyfor Chemical An
analysis (electron spectrochemical analysis) and C1S
From the peak areas of (carbon), Cl1S (chlorine) and O1S (oxygen), the vinyl chloride resin component on the particle surface was quantitatively analyzed based on the chlorine amount. -Equipment used: "JPS-90FX" manufactured by JEOL-Operating conditions: X-ray source (MgKα radiation), 12kV-15m
A ・ Scan speed: 200 ms / 0.1 eV / scan ・ Pass energy: 30 eV

(CPVC evaluation) (1) Measurement of chlorine content The measurement was carried out in accordance with JIS K 7229. (2) Measurement of Porosity and Pore Distribution Using a mercury intrusion porosimeter, the volume of mercury injected into 100 g of chlorinated vinyl chloride resin at 196 MPa was measured to determine the porosity. The porosity is a ratio of the porosity to the resin particle volume. In the pore distribution, the pressure was increased to 0 to 196 MPa in order to measure the porosity. At that time, the mercury intrusion amount was continuously measured, and the pore diameter distribution was measured. (3) Measurement of BET specific surface area The measurement was carried out in the same manner as the method for measuring the BET specific surface area of PVC.

(4) Measurement of absorbance CPVC was dissolved in tetrahydrofuran, and the concentration was 1 g / k.
g of the solution, and a spectrophotometer (“U-3” manufactured by Hitachi, Ltd.)
300 ”), the absorbance at a cell length of 1 cm, a measurement temperature of 23 ° C., and a wavelength of 235 nm was measured.

(5) Processability (Measurement of Gelation Temperature) Using a plastmill “Rheocord 90” manufactured by Haake, 55 g of the following resin composition was applied at a rotation speed of 40 rpm.
The kneading was performed while increasing the temperature at a rate of 5 ° C./min from 150 ° C., and the temperature at which the kneading torque was maximized was measured. The resin composition used was composed of 3 parts by weight of tribasic lead sulfate, 1 part by weight of dibasic lead stearate, and 10 parts by weight of MBS resin based on 100 parts by weight of CPVC.

(6) Thermal stability test The above resin composition was supplied to a kneader consisting of two 8-inch rolls and kneaded at a roll surface temperature of 205 ° C. CPV wrapped around
While turning back the C sheet, a small amount of the sheet was cut out every three minutes, the degree of coloring of the sheet was compared, and the thermal stability was determined by the time when the sheet turned blackish brown.

(7) Void volume From the pore distribution of CPVC, 0.001
The ratio of the void volume in the range of ０．１0.1 μm was calculated. (8) ESCA analysis Except that the measurement sample was CPVC, the method was the same as the method for ESCA analysis on the surface of PVC particles.

(Evaluation of Performance) (1) Vicat Softening Temperature Measured in accordance with JIS K 7206 (9.8 N load). (2) Charpy impact value Measured according to JIS K 7111. (3) Water absorption rate A pipe with a diameter of 20 mm was cut in the extrusion direction at a width of 20 mm,
Immerse in hot water of 0 ° C for 60 days, measure the change in weight,
The rate of change in weight was defined as the water absorption (%). (4) Long-term internal pressure creep test Measured with hot water at 90 ° C. in accordance with ASTM D2837.

(5) Surface Roughness (Rmax) The surface roughness was measured by the following method at each of eight places (45 ° intervals) in the circumferential direction of the inner surface of the molded product, and the average value was calculated to obtain Rmax. Was. That is, the measurement is repeated eight times in the axial direction (without returning), the average value of the six points excluding the maximum value and the minimum value is defined as the average roughness of the point, and the average value of the surface roughness of the eight points is calculated. The Rmax of the sample was used. -Measuring equipment: SURFCOM 1.63, manufactured by Toyo Seiki Co., Ltd.-Measurement speed: 0.3 mm / s-Evaluation length: 0.25 mm-Cutoff value: 0.08 mm-Tilt correction: R surface-Filter type: Gaussian-λs Filter: None ・ Preliminary drive length: Cut-off ratio / 3 ・ Calculation standard: JIS-'94

[0146]

As described above, the chlorinated vinyl chloride resin of the present invention and the method for producing the same have the above-mentioned constitutions, so that a chlorinated vinyl chloride resin having excellent heat stability and gelling property is provided. Since the chlorinated vinyl chloride resin molded article of the present invention has the above-described configuration, it has excellent heat resistance and impact strength, and the chlorinated vinyl chloride-based resin pipe of the present invention has the above-described configuration, and thus has high heat resistance. Since the pipe is high in temperature and has low water absorption, it can be suitably used as a pipe which is not broken by hot water, for example, a lining pipe such as a hot water supply pipe and a lining pipe, and a chemical resistant pipe. Furthermore,
The chlorinated vinyl chloride resin pipe of the present invention also has excellent smoothness and can prevent the propagation of bacteria and accumulation of rubber in the pipe, so that it can be suitably used for pure water piping for plants and the like. .

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA24 AA85 AB13 AD03 AD06 AF10Y AF15Y AF23Y BA01 BB06 BC05 4J100 AA02Q AA03Q AB02Q AC03P AC04Q AG04Q BB01H CA01 CA04 EA13 HA21 JA67

Claims (16)

[Claims] 1. A chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin, wherein the vinyl chloride resin has carbon atoms and chlorine atoms in particle surface analysis by electron spectrochemical analysis (ESCA). Has a peak ratio (chlorine element peak × 2 / carbon element peak) in 1S bond energy value (eV) of more than 0.6, and the chlorinated vinyl chloride resin has a chlorine content of 60 to 72% by weight. The porosity measured at a pressure of 196 MPa by the mercury intrusion method is 30 to 40% by volume, and the pressure is 0 by the mercury intrusion method.
In the pore volume distribution measured at ~ 196MPa, the
The void volume of 001 to 0.1 μm is 2 to 15 of the total void volume.
Chlorinated vinyl chloride resin characterized by volume%. 2. A chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin, wherein the vinyl chloride resin has a carbon atom and a chlorine atom in a particle surface analysis by an electron spectrochemical analysis (ESCA). Has a peak ratio (chlorine element peak × 2 / carbon element peak) in 1S bond energy value (eV) of more than 0.6, and the chlorinated vinyl chloride resin has a chlorine content of 60 to 72% by weight. The porosity measured at a pressure of 196 MPa by a mercury intrusion method is 30 to 40% by volume, and the BET specific surface area is 2 to 12%.
A chlorinated vinyl chloride resin characterized by having a m ² / g. 3. A chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin, wherein the vinyl chloride resin has carbon atoms and chlorine atoms in particle surface analysis by electron spectrochemical analysis (ESCA). Has a peak ratio (chlorine element peak × 2 / carbon element peak) in 1S bond energy value (eV) of more than 0.6, and the chlorinated vinyl chloride resin has a chlorine content of 60 to 72% by weight. The porosity measured at a pressure of 196 MPa by a mercury intrusion method is 30 to 40% by volume, and the pressure is 0 to 1 by a mercury intrusion method.
In the pore volume distribution measured at 96 MPa, 0.00
The void volume of 1 to 0.1 μm is 2 to 15% by volume of the total void volume, and the absorbance of 1 g / kg tetrahydrofuran solution (cell length 1 cm, measurement temperature 23 ° C.) is 235 nm wavelength.
Chlorinated vinyl chloride resin characterized in that the ratio is 0.8 or less. 4. A chlorinated vinyl chloride-based resin obtained by chlorinating a vinyl chloride-based resin, wherein the vinyl chloride-based resin has a carbon atom and a chlorine atom in a particle surface analysis by electron spectrochemical analysis (ESCA). Has a peak ratio (chlorine element peak × 2 / carbon element peak) in 1S bond energy value (eV) of more than 0.6, and the chlorinated vinyl chloride resin has a chlorine content of 60 to 72% by weight. The porosity measured at a pressure of 196 MPa by a mercury intrusion method is 30 to 40% by volume, and the BET specific surface area is ² to 12 m ^2.
/ G, and the absorbance of a 1 g / kg tetrahydrofuran solution (cell length 1 cm, measurement temperature 23 ° C.) was measured at a wavelength of 235 nm.
Chlorinated vinyl chloride resin characterized in that the ratio is 0.8 or less. 5. A chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin, wherein the vinyl chloride resin has carbon atoms and chlorine atoms in particle surface analysis by electron spectrochemical analysis (ESCA). Has a peak ratio (chlorine element peak × 2 / carbon element peak) in 1S bond energy value (eV) of more than 0.6, and the chlorinated vinyl chloride resin has a chlorine content of 60 to 72% by weight. The porosity measured at a pressure of 196 MPa by a mercury intrusion method is 30 to 40% by volume, and the pressure is 0 to 1 by a mercury intrusion method.
In the pore volume distribution measured at 96 MPa, 0.00
The pore volume of 1 to 0.1 μm is 2 to 15% by volume of the total pore volume, and the absorbance of 1 g / kg tetrahydrofuran solution (cell length 1 cm, measurement temperature 23 ° C.) is 235 nm.
A chlorinated vinyl chloride-based resin, wherein the chlorinated vinyl chloride-based resin is 0.2 or less. 6. A chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin, wherein the vinyl chloride resin has carbon atoms and chlorine atoms in particle surface analysis by electron spectrochemical analysis (ESCA). Has a peak ratio (chlorine element peak × 2 / carbon element peak) in 1S bond energy value (eV) of more than 0.6, and the chlorinated vinyl chloride resin has a chlorine content of 60 to 72% by weight. The porosity measured at a pressure of 196 MPa by a mercury intrusion method is 30 to 40% by volume, and the BET specific surface area is ² to 12 m ^2.
/ G, and the absorbance of the 1 g / kg tetrahydrofuran solution (cell length 1 cm, measurement temperature 23 ° C.) were measured at a wavelength of 235 nm.
A chlorinated vinyl chloride-based resin, wherein the chlorinated vinyl chloride-based resin is 0.2 or less. 7. A method for producing a chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin, wherein the vinyl chloride resin has a BET specific surface area of 1.3 to 8 m ² / g.
In the particle surface analysis by electron spectrochemical analysis (ESCA), the peak ratio (eV) of the carbon element and the chlorine element in the 1S bond energy value (eV) (chlorine element peak × 2)
/ Carbon element peak) exceeds 0.6, and in the chlorination, liquid chlorine or gaseous chlorine is introduced into a reactor in a state where a vinyl chloride resin is suspended in an aqueous medium. A method for producing a chlorinated vinyl chloride resin, which comprises introducing and reacting at a reaction temperature of 70 to 135 ° C. 8. The method for producing a chlorinated vinyl chloride resin according to claim 7, wherein the BET specific surface area of the vinyl chloride resin is 1.5 to ⁵ m ² / g. 9. The production of a chlorinated vinyl chloride resin according to claim 7, wherein the peak ratio in the particle surface analysis of the vinyl chloride resin by electron spectrochemical analysis (ESCA) exceeds 0.7. Method. 10. A chlorinated vinyl chloride-based resin molded article obtained by molding the chlorinated vinyl chloride-based resin according to claim 1, which is measured by a method according to JIS K7206. A chlorinated vinyl chloride resin molded product having a Vicat softening temperature of at least 145 ° C. under a load of 8 N. 11. A chlorinated vinyl chloride resin molded article obtained by molding the chlorinated vinyl chloride resin according to any one of claims 1 to 6, which is measured by a method in accordance with JIS K7206. A chlorinated vinyl chloride-based resin molded product having a Vicat softening temperature under a load of 8 N of 145 ° C. or more and a Charpy impact value of 10 kJ / m ² or more measured by a method according to JIS K 7111. 12. A chlorinated vinyl chloride resin molded article obtained by molding the chlorinated vinyl chloride resin according to claim 1, which is measured by a method according to JIS K7206. A chlorinated vinyl chloride resin molded article characterized in that the Vicat softening temperature under a load of 8 N is 145 ° C. or higher and the Charpy impact value measured by a method according to JIS K 7111 is 20 kJ / m ² or more. 13. A chlorinated vinyl chloride-based resin tube obtained by molding the chlorinated vinyl chloride-based resin according to claim 1, which is measured by a method according to JIS K7206. Vicat softening temperature under 8N load is 12
0 ° C. or higher, the water absorption after performing a hot water immersion test at 90 ° C. for 60 days is 1.5% or less, and ASTM D 28
In a long-term internal pressure creep test at 90 ° C. in accordance with No. 37, the breaking stress after a lapse of 1000 hours was 4.5 M.
A chlorinated vinyl chloride resin tube having a pressure of not less than Pa. 14. A chlorinated vinyl chloride-based resin tube obtained by molding the chlorinated vinyl chloride-based resin according to any one of claims 1 to 6, which is measured by a method in accordance with JIS K7206. Vicat softening temperature under 8N load is 12
0 ° C. or higher, the water absorption after performing a hot water immersion test at 90 ° C. for 60 days is 1.5% or less, and ASTM D 28
In a long-term internal pressure creep test at 90 ° C. in accordance with No. 37, the breaking stress after a lapse of 1000 hours was 4.5 M.
A chlorinated vinyl chloride resin tube having a surface roughness Rmax of not more than Pa and a surface roughness Rmax of not more than 5.0 μm. 15. The chlorinated vinyl chloride resin tube according to claim 13, which is a resin tube for hot water supply. 16. A lining pipe, characterized in that the chlorinated vinyl chloride resin pipe according to claim 13 is lined inside a metal pipe.